Lanthanide ions possess fascinating optical properties and their discovery, first industrial uses and present high technological applications are largely governed by their interaction with light. Lighting devices (economical luminescent lamps, light emitting diodes), television and computer displays, optical fibres, optical amplifiers, lasers, as well as responsive luminescent stains for biomedical analysis, medical diagnosis, and cell imaging rely heavily on lanthanide ions. This critical review has been tailored for a broad audience of chemists, biochemists and materials scientists; the basics of lanthanide photophysics are highlighted together with the synthetic strategies used to insert these ions into mono- and polymetallic molecular edifices. Recent advances in NIR-emitting materials, including liquid crystals, and in the control of luminescent properties in polymetallic assemblies are also presented. (210 references.)

Taking advantage of luminescent lanthanide ions

Lanthanide-based luminescent hybrid materials.

The free‐ion energy‐level schemes of the Pr3+, Nd3+, Pm3+, Sm3+, Dy3+, Ho3+, Er3+, and Tm3+ aquo ions have been determined from their absorption spectra in dilute acid solution at 25°. Energy‐level assignments were made by comparison with crystal spectra, and on the basis of correlations between calculated and observed band intensities. For most of the ions, it was possible to identify several transitions giving rise to bands at energies as high as 45 000–50 000 cm−1. Sufficient numbers of assignments were made to justify inclusion of the effects of configuration interaction in the calculation of the energy‐level parameters. Variation of the electrostatic, spin–orbit coupling, and configuration‐interaction parameters across the lanthanide series is examined.

Electronic Energy Levels in the Trivalent Lanthanide Aquo Ions. I. Pr3+, Nd3+, Pm3+, Sm3+, Dy3+, Ho3+, Er3+, and Tm3+

The Automated force field Topology Builder (ATB, http://compbio.biosci.uq.edu.au/atb) is a Web-accessible server that can provide topologies and parameters for a wide range of molecules appropriate for use in molecular simulations, computational drug design, and X-ray refinement. The ATB has three primary functions: (1) to act as a repository for molecules that have been parametrized as part of the GROMOS family of force fields, (2) to act as a repository for pre-equilibrated systems for use as starting configurations in molecular dynamics simulations (solvent mixtures, lipid systems pre-equilibrated to adopt a specific phase, etc.), and (3) to generate force field descriptions of novel molecules compatible with the GROMOS family of force fields in a variety of formats (GROMOS, GROMACS, and CNS). Force field descriptions of novel molecules are derived using a multistep process in which results from quantum mechanical (QM) calculations are combined with a knowledge-based approach to ensure compatibility (a...

An Automated Force Field Topology Builder (ATB) and Repository: Version 1.0.

Although luminescent complexes of lanthanide ions and organic ligands have been studied intensively, relatively little attention has been paid to the natural (or ‘radiative’) lifetime of the lanthanide centered luminescent state in these systems. Here, the applicability of the well-known Judd–Ofelt theory to the emissive properties of Eu3+ complexes is investigated. Moreover, it is demonstrated experimentally that the radiative lifetime of the 5D0 excited state of Eu3+ can be calculated directly from its corrected emission spectrum, without using Judd–Ofelt theory. We also discuss briefly the possibility of finding the natural lifetimes of lanthanide ions other than Eu3+.

The emission spectrum and the radiative lifetime of Eu3+ in luminescent lanthanide complexes

We have correlated the experimentally determined band intensities in the solution absorption spectra of the trivalent lanthanides with a theoretical expression derived by Judd. The spectra were measured in a single medium, dilute acid solution, and, in most cases, in the range ≈6000–50 000 cm−1. In general, the correlation between calculated and observed intensities was very good, even at higher energies. The variation of the intensity parameters over the series is discussed as is the somewhat unexpected degree of correlation obtained in the ultraviolet region.

Spectral Intensities of the Trivalent Lanthanides and Actinides in Solution. II. Pm3+, Sm3+, Eu3+, Gd3+, Tb3+, Dy3+, and Ho3+

The free‐ion energy level scheme of Eu3+ (aquo) to ∼40 000 cm−1 has been determined from the absorption spectrum of Eu3+ in dilute acid solution at 25°. Energy‐level assignments were made on the basis of correlations between calculated and observed intensities. A least‐squares fit of 26 J levels, including the effects of configuration interaction, gave an rms deviation of 40 cm−1. The parameter values were E1 = 5573.0, E2 = 26.708, E3 = 557.39, ζ4f = 1326.0, α = 25.336, β = − 580.25, and γ = 1155.7.

Electronic Energy Levels of the Trivalent Lanthanide Aquo Ions. III. Tb3

ELECTRONIC ENERGY LEVELS IN THE TRIVALENT LANTHANIDE AQUO IONS. I. Pr$sup 3+$, Nd$sup 3+$, Pm$sup 3+$, Sm$sup 3+$, Dy$sup 3+$, Ho$sup 3+$, Er$sup 3+$, AND Tm$sup 3$ .

/pdf/energy-levels-and-intensities-in-the-solution-absorption-o7xu5rv1w0.pdf

K. Rajnak

Papers

Electronic Energy Levels in the Trivalent Lanthanide Aquo Ions. I. Pr3+, Nd3+, Pm3+, Sm3+, Dy3+, Ho3+, Er3+, and Tm3+

Spectral Intensities of the Trivalent Lanthanides and Actinides in Solution. II. Pm3+, Sm3+, Eu3+, Gd3+, Tb3+, Dy3+, and Ho3+

Electronic Energy Levels of the Trivalent Lanthanide Aquo Ions. III. Tb3

ELECTRONIC ENERGY LEVELS IN THE TRIVALENT LANTHANIDE AQUO IONS. I. Pr$sup 3+$, Nd$sup 3+$, Pm$sup 3+$, Sm$sup 3+$, Dy$sup 3+$, Ho$sup 3+$, Er$sup 3+$, AND Tm$sup 3$ .

Energy levels and intensities in the solution absorption spectra of the trivalent lanthanides.